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Nanocalorimetry

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DOI: 10.1007/978-94-017-9780-1_208

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1
N

2 Nanocalorimetry experiments imposed when small systems are 30

involved. Indeed, most of the modern sensors are 31

3 Jean-Luc Garden and Olivier Bourgeois built to carry out measurements at the ultimate limit 32

4 Institut Néel CNRS-UJF, Grenoble, France of what can be detected by calorimetry on thin films or 33

very small volume samples. 34

In this entry, the key issues governing an experi- 35

5 Synonyms ment of nanocalorimetry are discussed. In particular, 36

for each point, recent experiments conducted in this 37

6 ac-Calorimetry; Attocalorimetry; Biocalorimetry; area over the world are presented. This will provide 38

7 Differential scanning calorimetry; Femtocalorimetry; a non-exhaustive overview of what is currently done in 39

8 Heat capacity; Isothermal calorimetry; Microcalorim- nanocalorimetry. Particular attention will be given 40

9 etry; Nanocalorimeter; Nanocalorimetric sensors; to micro- and nanofabrication technologies as well 41

10 Nanoscale thermal analysis; Nanotechnology; Relaxa- as highly sensitive thermal technique necessary 42

11 tion calorimetry; Thermodynamics of small systems; to achieve an experiment of nanocalorimetry. Here, 43

12 Thermometry bolometry is not discussed; despite its thematic 44

proximity; the measurement of radiation and possible 45

refrigeration at the mesoscopic scale has been 46

13 Definition described extensively in other works [19]. 47

14 Calorimetry is the part of thermodynamics which aims

15 to measure any quantity of heat (enthalpy, specific Nanocalorimetry 48

16 heat, heat release) stored, released or brought into

17 play in any state of matter, in a reaction, or in phase Introduction 49

18 transitions [27]. In calorimetry, thermal isolation is the major issue. 50

19 More precisely, the terminology of The heat capacity of a sample under study, or the 51

20 “Nanocalorimetry” may cover different concepts measurement of exchanges of energy between the 52

21 depending on the area of science where it is used. It sample and its environment, is properly measured 53

22 concerns any calorimetric method in which either the only if the sample is correctly isolated from its envi- 54

23 samples to be studied have a size in the range of the ronment (adiabatic conditions). In practice, the thermal 55

24 nanometer scale or the measured energies involved are isolation is not perfect, and one overcomes this prob- 56

25 of the order of the nanojoule or below. lem by calibrating correctly the thermal link between 57

26 Although these two types of definitions are very the sample and its surroundings. As discussed later in 58

27 different, they both have something in common. They this entry, the thermal relaxation rate, t, which deter- 59

28 are indeed concerned with the development of minia- mines the condition of adiabaticity, is a crucial param- 60

29 turized sensors and more generally with ultrasensitive eter for the selection of measurement methods adapted 61

B. Bhushan (ed.), Encyclopedia of Nanotechnology, DOI 10.1007/978-90-481-9751-4,

# Springer Science+Business Media B.V. 2012
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N 2 Nanocalorimetry

62 to the physics to be studied (see the section “Experi- elements. These elements are micro-machined in thin 111

63 mental Techniques”). This problem of thermal isola- layers of sub-micrometer thicknesses deposited by 112

64 tion is more problematic in nanocalorimetry because vacuum evaporation technique or by magnetron 113

65 the samples are very small in size and therefore have sputtering. Microphotolithography techniques are 114

66 small masses and thus very small heat capacities. used to shape the geometry of the sensitive elements 115

67 Therefore, to fulfill the requirement of adiabaticity, and define their impedances, and therefore define the 116

68 the experimentalist makes thin suspended membranes sensitivity of the calorimetric measurement. 117

69 micrometer thick that will support small objects to be Another major issue in calorimetry is the tempera- 118

70 studied (see Fig. 1). ture homogeneity of the sample and the addenda. 119

71 One of the advantage of working with membrane Indeed, the low thermal diffusivity of some samples 120

72 sensor is the reduction of addenda (the sample holder limits the dynamic of temperature variations during the 121

73 and the sensitive measuring elements are called measurement. The relaxation time of thermal diffusion 122

74 “addenda”); this is especially important when working in the sample and addenda, tdiff, also depends on the 123

75 with very small systems. The small thickness of the geometry of nanocalorimeters. In general, a thin layer 124

76 membrane reduces also the thermal coupling to the of gold, or highly diffusive material, is deposited by 125

77 outside providing then thermal isolation. Some mem- vacuum evaporation technique or sputtering on the 126

78 branes are structured to further limit the exchange of measurement area so that the temperature is as uniform 127

79 heat between the measurement area and the thermal as possible in the sample. Finally, the thin thickness of 128

80 bath. In this case, they look like micro-trampolines the membranes reduces the thermal coupling to the 129

81 suspended by arms that allow the passage of current outside providing then thermal isolation, while the 130

82 leads (see Fig. 2). isothermal layer ensures thermal homogeneity of the 131

83 Another point is that, since in the case of sensitive area. The experimental timescale Dtexp, the 132

84 nanocalorimetry the amount of energy to be measured timescale over which the thermal measurement occurs 133

85 is small, the resolution of the calorimetric measure- has to be slower than the diffusion time (to ensure 134

86 ment must be sufficiently high to access the expected a homogeneous temperature) and faster than the ther- 135

87 thermal properties. A first means to increase the signal- malization time of the sensing part to the heat bath. 136

88 to-noise ratio (SNR) of the measurement is to reduce This last point can be mathematically summarized by 137

89 the noise of the detected signals. In other words, one the two following inequalities: 138

90 must develop a low noise electronic chain adapted to

91 the chosen experimental technique and also adapted to tdiff <<Dtexp << t
92 the sensor converting temperature changes in measur-
93 able signals (usually voltage). This aspect, which con- where tdiff is the thermal diffusion time and t is the 139

94 cerns the sensitive measurements and thermometry, is thermal relaxation time. 140

95 discussed later on (see the section “Thermometry”).

96 A second way is to reduce significantly the heat capac- Thermometry 141

97 ity of sample holder and measuring devices (thermom- The basis of the measurement of heat is essentially 142

98 eters and heaters). based on the ability of the experimentalist to accurately 143

99 In this case, the use of nanotechnology and measure temperature. To obtain a sensitive measure- 144

100 microfabrication is indispensable for the realization ment of temperature, it requires access to a physical 145

101 of sample holder for which the heat capacity is at quantity X, which varies greatly with temperature. This 146

102 least equivalent (or smaller) than the sample heat large variation with temperature is characterized by 147

103 capacity being studied. The use of these technologies what is called the temperature coefficient X1 dX dT . 148

104 is crucial for measuring heat capacities of objects of A highly sensitive measurement of temperature varia- 149

105 very small size or for the detection of low energy in tion will allow a direct access to very small energy, 150

106 relevant thermodynamic transformations. Therefore, which is the case generally when nanosystems 151

107 micro- and nanotechnologies are essential keys are involved. The physical quantity X will be 152

108 to nanocalorimetry. This justifies the use of thin anything that can be accurately measured: a volume, 153

109 microfabricated membranes for thermal isolation

110 (see Fig. 3). Each membrane contains the sensitive
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Nanocalorimetry 3 N
154 a pressure, or an electrical quantity (capacitance, because its measurement does not require any electri- 202

155 resistance, etc. . .). cal current. 203

156 Some of the most used technique to measure tem- Thermocouple thermometry: A thermocouple is 204

157 perature in nanocalorimetric experiments are detailed composed of a junction between two different mate- 205

158 below. rials. A temperature difference between a “hot” and 206

159 Resistive thermometry: One of the most commonly a “cold” junction will be converted into a voltage 207

160 used physical quantities to measure a temperature is (Seebeck effect). The measurement of this voltage is 208

161 the resistance. The resistivity of pure metals is chang- a widespread way of measuring a temperature. How- 209

162 ing a lot with temperature from very high temperature ever, the amplitude in volt per Kelvin produced by 210

163 down to 30 K. Then, these metals will be perfect a usual thermocouple is small (of the order of magni- 211

164 thermometers in this temperature range. The most tude of several hundreds of microvolts per degree), it 212

165 common thermometer is platinum; this metal when needs at least a few hundred couples in a system called 213

166 elaborated in thin films geometry has a positive tem- thermopile to obtain sensitivities equivalent to those of 214

167 perature coefficient of resistance of about resistive thermometers. 215

3 1
R dT ¼ 3  10 K ; the resistance is decreasing
1 dR A thermopile is a device composed of plenty of 216
168

169 when the temperature is decreased (Fig. 4). Other thermocouples connected electrically in series and 217

170 materials have also a strong change of resistance with thermally in parallel. Each couple participates in the 218

171 temperature like semiconductor or like Anderson or total impedance of the sensor and therefore increases 219

172 Mott insulator. These materials have a huge increase of the thermal noise of electrons in conductors (Johnson– 220

173 resistance as the temperature is lowered because the Nyquist noise). The fact that it is not necessary to 221

174 electron transport is more and more limited as the polarize and thus generate thermal power in the sample 222

175 thermal activation is diminished. These materials (ger- to obtain a measuring signal is a major advantage of 223

176 manium, carbon, niobium silicon, niobium nitride) are this technique. 224

177 widely used as thermometer at low temperature. They When working close to room temperature, most 225

178 are much more efficient than metals below 40 K with calorimeters and differential nanocalorimeters use 226

179 temperature coefficient that can be above 1 K1! Tem- thermopile to measure directly the temperature differ- 227

180 peratures as low as few millikelvin, close to the abso- ence between the sample cell and a reference neutral 228

181 lute zero, may be measured using this type of cell (see DSC). In this case, the “hot” and “cold” 229

182 thermometry. The limitation comes from the applied junctions are perfectly thermally coupled to the sample 230

183 current necessary to measure the resistance; the Joule and reference, respectively (or vice versa). For zero 231

184 heating creates parasitic power. This dissipated power signal detection devices, two thermopiles connecting 232

185 may induce temperature gradients and then induces sample/thermal bath and reference/thermal bath, 233

186 error when estimating the real temperature of respectively, are mounted in opposition in order that 234

187 a nanosystem. same temperature elevations of the sample and refer- 235

188 Noise thermometry: Any electrons in a regular ences with respect to thermal bath gives approximately 236

189 resistance are subject to Brownian motion. This zero signal. Knowing the thermal link (thermal 237

190 Brownian motion takes its origin in the temperature exchange coefficient) between the sample and the ref- 238

191 activation. This movement of electrons gives birth to erence with respect to the surrounding, the voltage 239

192 a varying voltage across the resistor which is called the from the thermopile is proportional to the difference 240

193 Johnson–Nyquist noise. Due to its origin this noise is of heat flows (W) exchanged between the sample and 241

194 a function of the temperature through the reference with respect to thermal bath, respec- 242
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi tively. One prefers to present the converted signals 243
195 V ¼ 4kB TRDf , where kB is the Boltzmann constant,
196 T the temperature, R the resistance, and Df the fre- collected by thermopiles in watts rather than in Kelvin 244

197 quency window where this noise is measured. By mea- because their direct integration along time gives the 245

198 suring the voltage versus time, knowing the resistance, heat absorbed or released by the sample during the 246

199 one can deduce the temperature of the resistor R. This experiment of calorimetry. In conclusion, the thermo- 247

200 thermometry is not very sensitive but it has the major pile is the ideal element to detect differential temper- 248

201 advantage of not dissipating any spurious power ature or differential heat flow between two objects 249
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N 4 Nanocalorimetry

250 without direct generation of power in one or (and) the is the adiabatic calorimetry in which the sample and its 295

251 other of these objects. addenda are isolated as much as possible from their 296

environment. A thermal power of known value is sent 297

at a timescale much smaller than the thermal relaxation 298

252 Experimental Techniques time text. The measured temperature rise is inversely 299

proportional to the heat capacity of the sample (plus 300

253 Principle of Measurement addenda) 301

254 Calorimetry is the measurement of heat exchanges

R Dt
255 between a system for which the thermal properties Pdt
256 have to be studied and its environment (thermal DT ¼ 0
C
257 bath). There are two types of calorimetric measure-
258 ments. The first is the measurement of the specific heat. Then, it remains simply to change the temperature 302
259 In this case, the experimentalist provides a given heat of the thermal bath and carry out a new measurement in 303
260 flux to the sample and measures the resulting temper- order to have a final C (T) curve. In practice, 304
261 ature rise (Fig. 1c). The second concerns the measures adiabaticity is not perfect, and the heat exchange coef- 305
262 of energy released or absorbed by a sample during ficient has to be taken into account, and therefore 306
263 any transformations or physicochemical interaction at energy losses between the sample and the thermal 307
264 constant temperature; one speaks in this case about bath. This is especially true in nanocalorimetry 308
265 isothermal calorimetry. In all cases, the experiment because objects to be studied are small and therefore 309
266 of calorimetry consists in measuring a change in tem- their heat capacity is small to. It is therefore very 310
267 perature. Thermometry and the measurement electron- difficult to thermally isolate them, and the adiabatic 311
268 ics are therefore two essential elements for nanocalorimetry method cannot be implemented. Sci- 312
269 nanocalorimetry. The temperature sensor is then cho- entists have developed calorimetric techniques better 313
270 sen as a function of the particular experimental suited to the measurement of small samples to over- 314
271 methods used; the latter being in fact adapted to the come the problem of heat loss. They are presented in 315
272 physical phenomena that the experimentalist wishes to the following sections. 316
273 study.
274 Let us introduce two characteristic times which will Differential Scanning Calorimetry 317
275 be very useful in the rest of this entry. First the internal A second widespread calorimetric experimental tech- 318
276 thermalization time noted tint is defined; this time is nique is called differential scanning calorimetry (DSC) 319
277 related to the diffusion of heat inside the sample to be [11, 22]. It is a continuous method in which the sample 320
278 studied. Secondly, the external thermalization time temperature follows a temperature ramp imposed by 321
279 noted text is defined. This time is given by the ratio the experimentalist (Fig. 6). The fact that it is differ- 322
280 C/K where C is the heat capacity of the system and ential indicates that what is measured is directly the 323
281 K the thermal conductance of the link to the bath (see temperature difference between the sample and 324
282 Fig. 1). If a heat power is supplied to the sample at a neutral reference. However, one must keep in mind 325
283 a rate faster than the internal thermal time, then the that any calorimetric method can be conceived in dif- 326
284 temperature of the sample is not homogeneous (see ferential mode. In the case of DSC, differential heat 327
285 Fig. 5). On the other hand, if a power is supplied to capacity DC and differential heat flux DP (between 328
286 a sample over a very long time, then the external sample and reference) measured during the ramp tem- 329
287 thermal time will be dominant. A gradient of temper- perature obey the following equation: 330
288 ature will be established following an exponential law
289 between the sample and the heat bath as shown in the DP þ t dðDPÞ
290 Fig. 5. DC ¼ dt
b
291 Experimental Methods
where b is the scanning temperature rate and t the 331
292 Adiabatic Calorimetry
thermal relaxation time. This differential heat flux (or 332
293 Regarding the specific heat, various experimental
294 methods allow its measurement. The most traditional
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Nanocalorimetry 5 N
333 thermal power) is related to the differential tempera- frequency nanocalorimetric methods as seen in the 376

334 ture by means of the heat exchange coefficient K: following. 377

DP ¼ KDT Isothermal Calorimetry 378

A third widely used measurement method is called 379

335 Compared with the adiabatic calorimetry, here the Isothermal Calorimetry [26]. It consists of measuring 380

336 heat exchange coefficient K also plays a role at the absorption (or removals) of energy in a sample over 381

337 same level than the heat capacity C. The former is time at constant temperature (Fig. 7). Titration 382

338 measured by means of a prior calibration in quasi- nanocalorimetry is an experimental method issued 383

339 static mode where the above equation is valid. In from Isothermal Calorimetry in which a compound 384

340 DSC, the scanning rate b ¼ dT/dt, is an important A in solution (titrant) interacts with compound B in 385

341 factor since it determines the signal intensity. Indeed, solution (titrate), producing or absorbing energy at 386

342 the first equation above shows that for a given differ- constant temperature. If an aliquot (few percent in 387

343 ential heat capacity, the differential signal DP is for volume) of the titrant solution containing the molecule 388

344 a part proportional to this scanning rate. However, in A interacts with the solution containing the molecule 389

345 this case, the power of resolution of the measurement is B, then the experiment can be carried out N times to 390

346 reduced due to the presence of the second term reveal- achieve complete disappearance of B. In this way, 391

347 ing the dynamic of the DSC. Again, the thermal time through this type of experience, not only the enthalpy 392

348 constant plays a key role at high scanning rates. It of reaction between molecules A and B can be 393

349 should be noted that the above equations are only obtained (during the firsts interactions), but also, 394

350 valid for a large thermal diffusivity in the sample and thanks to the saturation curve DH ¼ f (N), the constant 395

351 the sample holder, so that the time constant of heat of reaction between A and B is obtainable, like for 396

352 diffusion (tint) does not become the limiting factor. acid-base chemical titrations. The constant of reaction 397

353 They are also valid under the assumption of perfect allows access to the Gibbs free energy at a certain 398

354 thermal symmetry of the calorimetric head (second- temperature. With calorimetric titration, the thermo- 399

355 order terms are not shown) [11, 22]. Classical DSC dynamic parameters DH, DG, and DS could be 400

356 based micro- and nanotechnologies are rare. Let us accessed for the reaction A/B which provide complete 401

357 mention SiN membrane DSC for heat capacity detec- thermodynamic data at determined temperatures. This 402

358 tion of nl-range liquid droplets [47] and MEMS-DSC technique is mainly used in chemistry, biochemistry, 403

359 device where protein folding processes are analyzed and biology [37]. Since in this field, firstly biochemical 404

360 via the measurement of differential heat capacity [44]. and biophysical reactions generally have relatively low 405

361 Fast speed DSC: In nanocalorimetry, the samples to energy values, and secondly available volumes of bio- 406

362 be studied are so small that the internal thermalization logical samples are generally reduced (simply because 407

363 time is not limiting. In this case, scientists have cir- they are expensive due to the cost of the synthesis) the 408

364 cumvent the problem of isolation of small samples in use of nanocalorimetry is a natural choice. In the past 409

365 using scanning rates with values going from about 104 decades, the development of isothermal titration 410

366 to 106 K/s. This new experimental technique, called nanocalorimeters has been increasing a lot [20, 45]. 411

367 “Fast Speed DSC,” has grown significantly in recent Another approach to induce interaction of A with B is 412

368 years. They use microsensors, typically SiN thin mem- to mix the two solutions in the sensitive area via two 413

369 branes, produced through micro- and nanotechnology differentiated liquid inputs. The mixture produces or 414

370 [1, 33, 42]). These very high speeds yield to high absorbs energy in the sensitive area which is detected 415

371 sensitivities and allow measurements of very thin by the sensor and then flows through a third flow output 416

372 films from 100 to 1,000 K [15, 31]. A last feature of path. One speaks about flow nanocalorimeters [24, 28, 417

373 these rapid calorimetric measurements is that, at such 30, 35, 49]. An original way of binding has been 418

374 high temperature rates, kinetics of studied thermal obtained by means of electrostatic mixing [41]. 419

375 event can be observed. This is also true for high- A major technical difficulty in the development of 420

isothermal titration or flow nanocalorimeters is the 421

need for a coupling of microfluidic techniques with 422

that of the microfabrication of nanosensors. Indeed, 423

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N 6 Nanocalorimetry

424 one needs to bring the various liquid reactants on the P0  t

T ¼ Tbath þ exp 
425 measurement area while maintaining the highest ther- K t
426 mal insulation of the same area. Certain isothermal
427 nanocalorimeter measures only the power or heat This decay is exponential and depends on the ratio 469

428 released or absorbed by a small biological object between the heat capacity of the sensor with the sample 470

429 already positioned (e.g., living cells) along time and the thermal conductance to the bath. The thermal 471

430 [8, 23, 43]. In the field of biocalorimetry, volumes of conductance can be estimated by other means, hence 472

431 analyzed samples comprise between few nanoliter and from the exponential decay the heat capacity can be 473

432 few microliter, and minimum detectable powers are deduced. This measurement is usually performed on 474

433 between few nanoWatt and few hundredth of a membrane where the thermometer and heater are 475

434 nanoWatt depending on the nanocalorimeters designs. lithographed. It is a sensitive method which may 476

435 Integration of power measured versus time yields to cover a large temperature range [12, 50]. One weak 477

436 minimum recorded energies from few tenth of point of this technique is that the measure is not based 478

437 nanoJoule to few microJoule (see tables showing per- on an oscillating method, and therefore the SNR is 479

438 formances of various isothermal calorimeters in Refs. degraded by the presence of thermal drift. This tech- 480

439 [6] and [28]). nique has been applied in some recent cases of specific 481

heat measurement on very small sensors at low tem- 482

440 Low Temperature Calorimetry perature [10, 39]. 483

441 Traditionally, at very low temperatures, the most used AC-calorimetry: In ac calorimetry, an input thermal 484

442 calorimetric method is the adiabatic calorimetry. How- power PðtÞ ¼ Pdc þ Pac constituted by a dc and a ac 485

443 ever, as the adiabatic nanocalorimetry is difficult to term is supplied to a system connected to a thermal 486

444 carry out at low dimension, scientists have developed bath by means of a thermal conductance of known 487

445 new techniques known as dynamic calorimetry tech- value [13, 25, 40, 51]. In focusing on the ac term 488

446 niques, which overcome the problem of heat loss. only, the corresponding oscillating temperature Tac is 489

447 There are two main different methods: the relaxation measured. At low frequencies the measurement is not 490

448 calorimetry and ac-calorimetry [5]. Relaxation calo- adiabatic or quasi-adiabatic, and at high frequencies 491

449 rimetry overcomes poor insulation in directly measur- the temperature of the sample is not homogeneous 492

450 ing the exponential decay of the temperature of anymore. This means that the thermal relaxation time 493

451 the sample compared to the thermal bath after a pulse and the thermal diffusion time have to be carefully 494

452 of power. Measuring the thermal conductance taken into account. However, in choosing the appro- 495

453 K is necessary to have the heat capacity. On contrary, priate frequency range, it is possible to circumvent the 496

454 ac-calorimetry depends only on the frequency of tem- problem of thermal insulation of small objects to be 497

455 perature oscillations to be placed in adiabatic condition measured by nanocalorimetry. It remains to design 498

456 or quasi-adiabatic conditions. The sample temperature a calorimetric device with an appropriate working 499

457 oscillates at a frequency such that no heat loss holds frequency range. The frequency of the temperature 500

458 over one period of oscillation. In this case, it is not oscillation has to be faster than the relaxation time to 501

459 necessary to measure K. These different experimental the heat bath text (adiabatic condition) and slower than 502

460 techniques suitable for nanocalorimetry are described the diffusion time in the sensor tint. Under these cir- 503

461 below. cumstances, the heat capacity of the sample is simply 504

462 Relaxation calorimetry: Relaxation calorimetry is obtained by the ratio of the ac power on the ac 505

463 to apply a heat pulse on the sensitive area of a sensor. temperature: 506

464 An increase in the temperature of the sample appears;

465 this increase will be faster than heat leak because the Pac
C¼
466 internal diffusion time is very short. The technique ioTac
467 involves recording the decrease of the temperature
468 sensor over time: The measured heat capacity is actually a complex 507

number with real and imaginary components of differ- 508

ent physical meaning. These are obtained by means of 509

the measure of either the amplitude or the phase of the 510

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Nanocalorimetry 7 N
511 oscillating temperature. This method is particularly is only related to the thermal conductance. If the mea- 553

512 sensitive because locking-amplifiers with narrow surement is made as a function of the frequency, the 554

513 bandwidth filter can be used for oscillating temperature heat capacity can be extracted through the estimation 555

514 recording but also because dc or low frequency thermal of the thermalization time t ¼ KC . 556

515 drifts are less important. Heat capacity resolutions The purely electrical term oscillating at frequency f, 557

516 DC/C of the order of 105 to 104 are currently which is much larger than the 3f component, has gen- 558

517 obtained while in relaxation calorimetry or other erally to be removed using a Wheatstone bridge circuit, 559

518 methods resolutions lay between 103 and 102. otherwise the quality of the measurement will suffer. 560

519 Thus, ac-calorimetry is a technique particularly This method, non-adiabatic by principle, was used to 561

520 adapted to nanocalorimetry because, on one side it measure the thermal properties of material of very 562

521 allows measures on small objects, and on another small thermal diffusivity for which a frequency depen- 563

522 side it allows measurement in the nanoJoule/Kelvin dence of the specific heat was expected. It has, for 564

523 or nanoJoule/picoJoule ranges [16, 32]. Although ac example, been successfully used to study the fre- 565

524 calorimetry has been developed in the field of low quency-dependent specific heat at the glass transition 566

525 temperature physics [34]), for few decades it has of some glass formers over several decades of fre- 567

526 been adapted to different temperature ranges in several quency [2]. Depending on the geometry of the couple 568

527 domains of research (magnetic films, biological transducer with sample, the thermal effusivity c  k 569

528 objects, polymers, etc. . .) where the detection of fine (product of specific heat by thermal conductivity) is 570

529 phase transitions or phase transformations were measured or, upon particular geometrical conditions, 571

530 researched [17, 18, 46]. More precisely, the record in the thermal conductivity k is directly measured at low 572

531 sensitivity was obtained in attojoule calorimetry frequency (see equations above) [52]. In 573

532 (1018 J) which allowed access to complete new phys- nanocalorimetry, this method has been successfully 574

533 ics [3]. The principal inconvenient of ac-calorimetry is applied to the measurement of the thermal conductiv- 575

534 the useable frequency range limited to no more than ity of crystalline silicon wires of nanometric sizes for 576

535 one or two decades when measurement of the dynamic which phonon-blocking effects were observed at very 577

536 of the studied system via C(o) is wanted. This disad- low temperatures [4, 21]. Recent experiments use the 578

537 vantage is avoided in another dynamic calorimetric 3o method for thermal properties measurement of nl 579

538 method called 3o method (Fig. 8). liquid-like samples [9, 36]. 580

Unconventional methods: measurement of caloric 581

539 Other Methods curve. In this technique developed for the in-flight 582

540 3o-method. In the 3o method, the thermal power that measurement of clusters (hundred of atom), one uses 583

541 generates temperature oscillations in the sample is the photofragmentation of the clusters by a laser beam 584

542 provided by the thermometer itself. A current of fre- to estimate the internal energy U as a function of 585

543 quency f passes through the thermometer-like heater temperature. The clusters ions are selected using 586

544 resistance (called the transducer), which produces a mass spectrometer and thermalized in helium gas. 587

545 a thermal power oscillating at frequency 2f due to Then they are irradiated by a laser, the fragments 588

546 Joule effect. As the transducer temperature varies at produced are analyzed by a second mass spectrometer. 589

547 that frequency, this results in a 3f term which contains Their number depends directly on the inner energy of 590

548 all the thermal information of the sample [2, 14]: each clusters, hence its measurement  gives the
 internal 591

energy of the cluster. Its derivative C ¼ @U @T will give 592

P0 P0 the heat capacity of the clusters ions (see Refs. [7, 38]). 593
dTac ¼ qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi or dTac ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffi Melting point and heat capacity of cluster of 140 atoms 594
K 1 þ ðotÞ2 2oCK
or less could be measured using this technique, 595

a performance never equaled with other techniques. 596

549 The two above equations apply depending on the Others unconventional methods of nano- and micro- 597

550 geometrical design of the sensor. o is the pulsation, calorimetry exist but are not described in this brief 598

551 related to the frequency through o ¼ 2pf . At very low entry. 599

552 frequency, the amplitude of the temperature oscillation

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N 8 Nanocalorimetry

600 Micro- and Nanosensors If one wants to apply nanocalorimetry technique at 647

low or very low temperature, SiN is not the best choice. 648

601 It is the need to do thermodynamic measurements on As it can be seen in the Table 1, the heat capacity is 649

602 specific physical or chemical nanosystem that will high as compared to single crystal silicon. Then the 650

603 determine what type of sensor that must be developed fabrication of silicon membrane is more appropriate 651

604 for nanocalorimetry. Secondly, the choice of the exper- and should be preferred. Moreover, the structuring of 652

605 imental technique (as detailed in the previous section) the membrane will be absolutely necessary to create 653

606 will also influence the conception of the sensing part. a well-defined isotherm. Indeed, the thermal conduc- 654

607 Several examples of nanocalorimeter based on micro- tance of silicon (or SiN) is still high below 10 K, and 655

608 or nanofabrication are shown below where the best then a proper thermal isolation lies in suspending 656

609 results have been obtained in terms of sensitivity and/ a membrane through isolated arms (see Fig. 2a or b). 657

610 or resolution. Great care must be taken in the choice of In Fig. 10, examples (c), (g), and (i) are silicon mem- 658

611 materials along with the geometry of the system (ther- brane for isothermal flow-through or small-volume- 659

612 mometry and heater); it will fully determine the ther- liquid nanocalorimetric measurements. 660

613 mal performance of the sensor. Two main parameters

614 should orient the choice of materials for the sample Polymer Membranes 661

615 holder: small heat capacity and a complete absence of In nanocalorimetry, thin polymer membranes are also 662

616 phase change in the working temperature area to avoid used to insure good thermal insulation of the measure- 663

617 spurious signal coming from the holder. The geometry ment area. This type of membrane is mostly used for 664

618 will be chosen to reduce the leak to the heat bath or to medium to high temperatures because of the low ther- 665

619 control it through a dedicated thermal link. Thermal mal conductivity of polymers (see Table 1). At very 666

620 data of the main materials used for manufacturing low temperatures, they are less attractive because their 667

621 sensors are summarized in Table 1. This table will be heat capacity is very high (see Table 1). To ensure 668

622 fruitfully used during the design of a new sensor uniformity of temperature in these sensors, the low 669

623 depending of its future working temperature range or thermal diffusivity of these materials is generally elim- 670

624 its particular specifications (materials compatibility). inated through the deposition of a thin layer of metal 671

625 The first attempt to measure the heat capacity of diffusing heat over the entire surface of the sensitive 672

626 thin films was done by G.D. Zally et al. [48]. He built area (e.g., gold, aluminum, silver). Figures 2d, f and 673

627 a calorimeter based on a very thin pyrex membrane 10a, d, h are examples of polymer membranes for 674

628 where thermometer and heater were attached. Since experiments of ac-nanocalorimetry or isothermal 675

629 this attempt, numerous different sensors have been nanocalorimetry on thin magnetic films, thin polymer 676

630 built in various materials from silicon, silicon nitride, films, and low volumes chemical or biological objects 677

631 glass to polymer. Some of them are detailed below. or reactions. The thickness of these membranes can 678

range from a few hundreds of nanometers to several 679

632 Silicon, Silicon Nitride, or Diamond Membranes tens of micrometers. The use of micro- and nano- 680

633 As mentioned above, the choice of the materials is technologies is obviously necessary to deposit and 681

634 given by the specification of the experiment to be lithographically machined sensing elements on the 682

635 performed. The best material for application in membrane, as well as a possible step of membrane 683

636 a wide temperature range (from 40 K to 1,000 K) is, design through dry etching techniques (e.g., reactive 684

637 for sure, silicon nitride (SiN). This amorphous material ion etching or oxygen plasma). 685

638 is totally inert in that temperature window and can be

639 easily manipulated. Fabrication of membrane out of
640 SiN is masterized in all cleanrooms in the world using Conclusion 686

641 chemical etching of silicon by KOH (see the sketch in

642 Fig. 9). Thermometer and heater can be lithographed In that not complete review, various experimental 687

643 on top, which permits the measurement of thermal methods named “nanocalorimetry” have been 688

644 properties. The design of the heat link and the choice presented. It has been shown that it concerns all calo- 689

645 of materials for the transducers will set the perfor- rimetric method for which the dimensions of the 690

646 mance of the calorimeter. objects studied are in the order of magnitude of 691
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Nanocalorimetry 9 N
692 nanometer, or measured energy or power are in 5. Bourgeois, O.: Thermal nanosystems and nanomaterials. 738

693 the range of nanojoule or nanowatt. The review has Book series: Topics in applied physics, pp. 537–567. 739
Springer, Berlin (2009) 740
694 been based on numerous examples of 6. Braissant, O., Wirz, D., G€opfert, B., Daniels, A.U.: Biomed- 741
695 nanocalorimeters existing in the literature from low ical use of isothermal microcalorimeters. Sensors 10, 9369– 742
696 temperature to room temperature with application in 9383 (2010) 743

697 condensed matter, chemistry, biophysics, or biology in 7. Breaux, G.A., Benirschke, R.C., Sugai, T., Kinnear, B.S., 744
Jarrold, M.F.: Hot and solid gallium clusters: Too small to 745
698 general. The aspect of micro- and nanofabrication, melt. Phys. Rev. Lett. 91, 215508 (2003) 746
699 essential for the achievement of nanocalorimetric 8. Chancellor, E.B., Wikswo, J.P., Baudenbacher, F., 747
700 devices, has been emphasized as well as the impor- Radparvar, M., Osterman, D.: Heat conduction calorimeter 748

701 tance of sensitive instrumentation, electronic condi- for massively parallel high throughput measurements with 749
picoliter sample volumes. Appl. Phys. Lett. 85, 2408–2410 750
702 tioning, and the choice of materials for the thermal (2004) 751
703 detectors. 9. Choi, S.R., Kim, D.: Real-time thermal characterization of 752
704 Calorimetry is by essence a universal method of 12 nl fluid samples in a microchannel. Rev. Sci. Instrum. 79, 753

705 measurement, covering by this way a wide spectrum 064901 (2008) 754
10. Chung Fon, W., Schwab, K.C., Worlock, J.M., Roukes, M.L.: 755
706 of different researches. The emergence of Nanoscale, phonon-coupled calorimetry with sub-attojoule/ 756
707 nanocalorimetry in recent decades has allowed the Kelvin resolution. Nano Lett. 5, 1968 (2005) 757
708 exploration of new and original fields of research. 11. Claudy, P.: Analyse Calorimétrique Différentielle. Lavoi- 758

709 With the evolution of modern micro- and sier, Paris (2005) 759
12. Cooke, D.W., Michel, K.J., Hellman, F.: Thermodynamic 760
710 nanofabrication technologies, many new develop- measurements of submilligram bulk samples using a mem- 761
711 ments will appear especially toward more sensitive brane-based “calorimeter on a chip”. Rev. Sci. Instrum. 79, 762
712 sensor especially in biophysics. Significant room for 053902 (2008) 763

713 improvement still exists in many areas of nanoscience, 13. Corbino, O.M.: Thermal oscillations in lamps of thin fibers 764
with alternating current flowing through them and the 765
714 which makes nanocalorimetry quite an open subject of resulting effect on the rectifier as a result of the presence 766
715 research. of even-numbered harmonics. Phys. Z. 11, 413–417 (1910) 767
14. Corbino, O.M.: Periodic resistance changes of fine metal 768
threads, which are brought together by alternating streams 769
as well as deduction of their thermo characteristics at high 770
716 Cross-References temperatures. Phys. Z. 12, 292–295 (1911) 771
15. Efremov, M.Y., Olson, E.A., Zhang, M., Schiettekatte, F., 772
717 ▶ Biosensors Zhang, Z.S., Allen, L.H.: Ultrasensitive, fast, thin-film dif- 773

718 ▶ Nanotechnology ferential scanning calorimeter. Rev. Sci. Instrum. 75, 179– 774
191 (2004) 775
719 ▶ Thermal Actuators 16. Fominaya, F., Fournier, T., Gandit, P., Chaussy, J.: 776
720 ▶ Thermal Conductivity and Phonon Transport Nanocalorimeter for high resolution measurements of low 777
721 ▶ Thermoelectric Heat Convertors temperature heat capacities of thin films and single crystals. 778
Rev. Sci. Instrum. 68, 4191–4195 (1997) 779
17. Garden, J.-L., Château, E., Chaussy, J.: Highly sensitive ac 780
nanocalorimeter for microliter-scale liquids or biological 781
722 References samples. Appl. Phys. Lett. 84, 3597–3599 (2004) 782
18. Garden, J.-L., Guillou, H., Lopeandia, A.F., Richard, J., 783
723 1. Anahory, Y., Guihard, M., Smeets, D., Karmouch, R., Heron, J.-S., Souche, G.M., Ong, F.R., Vianay, B., 784
724 Schiettekatte, F., Vasseur, P., Desjardins, P., Hu, L.A., Bourgeois, O.: Thermodynamics of small systems by 785
725 Allen, L.H., Leon-Gutierrez, E., Rodriguez-Viejo, J.: Fabri- nanocalorimetry: From physical to biological nano-objects. 786
726 cation, characterization and modeling of single-crystal thin Thermochim. Acta 492, 16–28 (2009) 787
727 film calorimeter sensors. Thermochim. Acta 510, 126–136 19. Giazotto, F., Heikkil€a, T.T., Luukanen, A., Savin, A.M., 788
728 (2010) Pekola, J.P.: Opportunities for mesoscopics in thermometry 789
729 2. Birge, N.O., Dixon, P.K., Menon, N.: Specific heat spec- and refrigeration: Physics and applications. Rev. Mod. Phys. 790
730 troscopy: Origins, status and applications of the 3 omega 78, 217 (2006) 791
731 method. Thermochim. Acta 304(305), 51–66 (1997) 20. Hakala, T.K., Toppari, J.J., Torma, P.: A hybrid method for 792
732 3. Bourgeois, O., Skipetrov, S., Ong, F., Chaussy, J.: Attojoule calorimetry with subnanoliter samples using Schottky junc- 793
733 calorimetry of mesoscopic superconducting loops. Phys. tions. J. Appl. Phys. 101, 034512 (2007) 794
734 Rev. Lett. 94, 057007 (2005) 21. Heron, J.-S., Bera, C., Fournier, T., Mingo, N., Bourgeois, O.: 795
735 4. Bourgeois, O., Fournier, Th, Chaussy, J.: Measurement of Blocking phonons via nanoscale geometrical design. Phys. 796
736 the thermal conductance of silicon nanowires at low tem- Rev. B 82, 155458 (2010) 797
737 perature. J. Appl. Phys. 101, 016104 (2007)
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798 22. H€ohne, G.W.H., Hemminger, W.F., Flammersheim, H.-J.: point and heat capacity for a free cluster of 139 sodium 852
799 Differential scanning calorimetry, 2nd edn. Springer, Ber- atoms. Phys. Rev. Lett. 79, 99 (1997) 853
800 lin/Heidelberg (2010) 39. Suh, K.S., Kim, J.W., Kim, H.J., Park, Y.D., Kim, K.H.: 854
801 23. Johannessen, E.A., Weaver, J.M.R., Bourova, L., Svoboda, P., Enhanced accuracy in a silicon-nitride-membrane-based 855
802 Cobbold, P.H., Cooper, J.M.: Micromachined microcalorimeter with variation of lateral layout. 856
803 nanocalorimetric sensor for ultra-low-volume cell-based Thermochim. Acta 490, 1–7 (2009) 857
804 assays. Anal. Chem. 74, 2190–2197 (2002) 40. Sullivan, P.F., Seidel, G.: steady-state ac-temperature calo- 858
805 24. K€ohler, J.M., Zieren, M.: Micro flow calorimeter for rimetry. Phys. Rev. 173, 679–685 (1968) 859
806 thermoelectrical detection of heat of reaction in small vol- 41. Torres, F.E., De Bruyker, D., Bell, A.G., Wolkin, M.V., 860
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808 25. Kraftmakher, Y.: Modulation calorimetry and related tech- Recht, M.I., Schweizer, S., Scott, L.G., Ho, J.H., Elrod, S.A., 862
809 niques. Phys. Rep. 356, 1–117 (2002) Schultz, P.G., Lerner, R.A., Bruce, R.H.: Enthalpy arrays. 863
810 26. Ladbury, J.E., Chowdhry, B.Z. (eds.): Biocalorimetry, Proc. Nat. Acad. Sci. 101, 9517–9522 (2004) 864
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812 Wiley, Chichester (1998) various applications. Thermochim. Acta 432, 192–201 866
813 27. Lavoisier, A., de Laplace, P.S.: Mémoire sur la chaleur, (2005) 867
814 p. 355. Académie des Sciences, Paris (1780) 43. Verhaegen, K., Baert, K., Simaels, J., Van Driessche, W.: A 868
815 28. Lee, W., Fon, W., Axelrod, B.W., Roukes, M.L.: High- high-throughput silicon microphysiometer. Sensor. Actuat. 869
816 sensitivity microfluidic calorimeters for biological and 82, 186–190 (2000) 870
817 chemical applications. Proc. Nat. Acad. Sci. 106, 15225– 44. Wang, L., Wang, B., Lin, Q.: Demonstration of MEMS- 871
818 15230 (2009) based differential scanning calorimetry for determining 872
819 29. Lerchner, J., Wolf, A., Wolf, G., Baier, V., Kessler, E., thermodynamic properties of biomolecules. Sensor. Actuat. 873
820 Nietzsch, M., Kr€ ugel, M.: A new micro-fluid chip calorim- B 134, 953–958 (2008) 874
821 eter for biochemical applications. Thermochim. Acta 445, 45. Xu, J., Reiserer, R., Tellinghuisen, J., Wikswo, J.P., 875
822 144–150 (2006) Baudenbacher, F.J.: A microfabricated nanocalorimeter: 876
823 30. Lerchner, J., Wolf, A., Schneider, H.-J., Mertens, F., Design, characterization, and chemical calibration. Anal. 877
824 Kessler, E., Baier, V., Funfak, A., Nietzsch, M., Krugel, M.: Chem. 80, 2728–2733 (2008) 878
825 Nano-calorimetry of small-sized biological samples. 46. Yao, H., Ema, K., Fukada, H., Takahashi, K., Hatta, I.: ac 879
826 Thermochim. Acta 477, 48–53 (2008) nanocalorimeter for measuring heat capacity of biological 880
827 31. Lopeandia, A.F., Valenzuela, J., Rodriguez-Viejo, J.: Power macromolecules in solution. Rev. Sci. Instrum. 74, 4164– 881
828 compensated thin film calorimetry at fast heating rates. 4168 (2003) 882
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830 32. Lopeandia, A.F., Andre, E., Garden, J.-L., Givord, D., Foucaran, A.: MEMS scanning calorimeter with serpentine- 884
831 Bourgeois, O.: Highly sensitive parylene membrane-based shaped platinum resistors for characterizations of 885
832 ac-calorimeter for small mass magnetic samples. Rev. Sci. microsamples. J. Microelectromech. Syst. 18, 414–423 886
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835 batic thin-film (chip) nanocalorimetry. Thermochim. Acta superconducting thin films of amorphous BiSb. Phys. Rev. 889
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838 Thin-film alternating current nanocalorimeter for low tem- integrated microfluidic channels. Biosens. Bioelectron. 19, 892
839 peratures and high magnetic fields. Rev. Sci. Instrum. 76, 1733–1743 (2004) 893
840 043906 (2005) 50. Queen, D.R., Hellman, F.: Thin film nanocalorimeter for 894
841 35. Nam, S.K., Kim, J.K., Cho, S.C., Lee, S.K.: Design and heat capacity measurements of 30 nm films. Rev. Sci. 895
842 characterization of a high resolution microfluidic heat flux Instrum. 80, 063901 (2009) 896
843 sensor with thermal modulation. Sensors 10, 6594–6611 51. Tagliati, S., Rydh, A.: Absolute accuracy in membrane- 897
844 (2010) based ac nanocalorimetry. Thermochim. Acta 522, 66–71 898
845 36. Park, B.K., Park, J., Kim, D.: Three-omega method to mea- (2011) 899
846 sure thermal properties of subnanoliter liquid samples. Rev. 52. Cahill, D.G.: Thermal-conductivity measurement from 30- 900
847 Sci. Instrum. 81, 066104 (2010) K to 750-K - the 3-omega method. Rev. Sci. Instrum. 61, 901
848 37. Russell, D.J., Hansen, L.D.: Calorimeters for biotechnology. 802–808 (1990) 902
849 Thermochim. Acta 445, 151–159 (2006)
850 38. Schmidt, M., Kusche, R., Kronmuller, W., von Issendorf, B.,
851 Haberland, H.: Experimental determination of the melting
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Nanocalorimetry 11 N
t1:1 Nanocalorimetry, Table 1 Thermal parameters for various materials from high temperature to very low temperature. The thermal
conductivity is given in W/cm K and the specific heat in J/g K
t1:2 Si SiN Pure copper Polymer (PTFE) Glass
t1:3 c k c k c k c k c k
t1:4 1,000 K 8.2 0.3 4 0.2 0.5 4 NA NA 3 2.102
t1:5 300 K 6.7 1.5 2 0.1 0.3 4 0.9 3 103 1 102
t1:6 100 K 2.5 8 1 4.102 0.25 5 0.3 2 103 0.6 8.103
t1:7 10 K 2.103 0.3 103 6.103 8.104 160 0.18 103 6.103 103
t1:8 1K 5.107 103 106 5.104 105 40 10 3
7.105 7.106 5.104
t1:9 0.1 K 1011 NA 109 NA 106 0.4 NA NA 8.108 105

Nanocalorimetry, Fig. 1 Thermal schemes for calorimetric
experiments (a) a quantity of heat DQ is released in the sample,
an increase of temperature will appear. This system is assumed
to be infinitely isolated from the heat bath. (b) An external heat is
supplied to the sample also infinitely isolated from the heat bath.
By measuring the increase of temperature we will get access to
the heat capacity of the sample (adiabatic calorimetry). (c) The
sample is linked to the heat bath through a thermal conductance
K; a thermometer and a heater allow the measurement of the
thermal properties (C and K)
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N 12
a b
d e
Nanocalorimetry, Fig. 2 Various sensors made in silicon,
silicon nitride, or polymer. (a) Silicon membrane for very low
temperature heat capacity measurement by ac calorimetry [3].
(b) Silicon nitride sensor made by e-beam lithography used for
relaxation calorimetry [10]. (c) Silicon nitride sensor used for
fast scanning calorimetry [31]. (d) Polyparaxylylene membrane
Nanocalorimetry, Fig. 3 Scheme of the principle of
a nanocalorimetric measurement on membrane
Nanocalorimetry
c
for phase transition detection in thin magnetic films around
100 K [32]. (e) Silicon nitride sensor used for relaxation
calorimetry over a wide range of temperature (Cooke 2010).
(f) Polyimide membrane for heat capacity measurement of thin
polymer films at ambient temperature [18]
Nanocalorimetry, Fig. 4 Variation of resistance versus tem-
perature in the cases of metals and semiconductors
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Nanocalorimetry 13 N

Nanocalorimetry, Fig. 5 Illustration of the two significant

timescales in a nanocalorimetric experiment

Nanocalorimetry, Fig. 6 Thermal scheme for DSC experi-

ment. One cell contains the sample and the other cell contains
a neutral reference. During the scanning temperature rate the
temperature difference (or heat flux difference) is recorded as
a function of time
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N 14 Nanocalorimetry

Nanocalorimetry,
Fig. 7 Thermal scheme
for isothermal calorimetry
experiment. The power
necessary to maintain the
temperature of the sample at
a constant value is represented
versus time. The integration of
this power provides the energy
absorbed or dissipated by the
sample at such temperature

Nanocalorimetry, Fig. 9 Example of microfabrication proce-

dure of a suspended membrane of SiN. 1 Spinning of resist
Nanocalorimetry, Fig. 8 Schemes of the 3o method with and photolithography, 2 remove the resist, 3 chemical etching
the thermal wave in the plane (perpendicular to the transducer) of silicon with KOH, 4 photolithography of the transducer,
(a) or along the sample (parallel to the transducer) (b) 5 deposition of the transducer, 6 lift-off
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Nanocalorimetry 15 N
a b c

d e f

g h b i c

Nanocalorimetry, Fig. 10 Various sensors for isothermal
or biological liquid-sample nanocalorimetric experiments.
(a) Parylene membrane for isothermal chemical and biological
interactions [28], (b) silicon sensor for isothermal chemical and
biological interactions (Photograph courtesy www.xensor.nl,
[42]), (c) silicon nitride sensor for small-volume-liquid calori-
metric detection [20], (d) polyimide membrane for electrostatic-
liquid-mixing calorimetric detection [41], (e) silicon
microfluidic chamber for flow-through isothermal calorimetry
[29], (f) glass microfluidic reaction chamber for flow-through
calorimetry [49], (g) silicon nitride membrane for small-volume-
liquid calorimetric detection [8], (h) micro-posts sustained
polyimide membrane for small-volume-liquid calorimetric
detection [18], (i) silicon nitride suspended sensor for isothermal
detection of living cells [23]

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